Preface |
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xvi | |
To the Student |
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xxv | |
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1 | (12) |
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1.1 How Electrons Are Arranged In Atoms |
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2 | (1) |
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1.2 Ionic And Covalent Bonding |
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3 | (4) |
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4 | (1) |
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5 | (2) |
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1.3 Carbon And The Covalent Bond |
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7 | (1) |
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1.4 Carbon--Carbon Single Bonds |
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8 | (1) |
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9 | (2) |
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1.6 Multiple Covalent Bonds |
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11 | (1) |
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12 | (1) |
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13 | (1) |
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A CLOSER LOOK AT ...Green Chemistry |
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13 | (32) |
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1.9 Writing Structural Formulas |
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14 | (2) |
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1.10 Abbreviated Structural Formulas |
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16 | (2) |
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18 | (2) |
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20 | (1) |
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21 | (2) |
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1.14 The Orbital View Of Bonding; The Sigma Bond |
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23 | (1) |
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1.15 Carbon Sp3 Hybrid Orbitals |
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24 | (1) |
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1.16 Tetrahedral Carbon; The Bonding In Methane |
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25 | (2) |
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1.17 Classification According To Molecular Framework |
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27 | (3) |
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27 | (1) |
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1.17.b Carbocyclic Compounds |
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28 | (1) |
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1.17.c Heterocyclic Compounds |
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28 | (2) |
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1.18 Classification According To Functional Group |
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30 | (6) |
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32 | (4) |
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2 Alkanes and Cycloalkanes; Conformational and Geometric Isomerism |
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36 | (9) |
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2.1 The Structures Of Alkanes |
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37 | (1) |
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2.2 Nomenclature Of Organic Compounds |
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38 | (1) |
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2.3 Iupac Rules For Naming Alkanes |
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39 | (2) |
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2.4 Alkyl And Halogen Substituents |
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41 | (2) |
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2.5 Use Of The Iupac Rules |
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43 | (1) |
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44 | (1) |
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A CLOSER LOOK AT ...Natural Gas AA |
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2.7 Physical Properties Of Alkanes And Nonbonding Intermolecular Interactions |
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45 | (1) |
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A CLOSER LOOK AT ...Hydrogen Bonding |
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46 | (9) |
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2.8 Conformations Of Alkanes |
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47 | (2) |
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2.9 Cycloalkane Nomenclature And Conformation |
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49 | (5) |
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2.10 Cis-Trans Isomerism In Cycloalkanes |
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54 | (1) |
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A WORD ABOUT ...Isomers---Possible and Impossible |
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55 | (3) |
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2.11 Summary Of Isomerism |
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56 | (1) |
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2.12 Reactions Of Alkanes |
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56 | (2) |
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2.12.a Oxidation and Combustion; Alkanes as Fuels |
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57 | (1) |
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A WORD ABOUT ...Alternative Energy: The Benefits of Hydrogen |
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58 | (2) |
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2.12.b Halogenation of Alkanes |
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59 | (1) |
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A WORD ABOUT ...Methane, Marsh Gas, and Miller's Experiment |
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60 | (16) |
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2.13 The Free-Radical Chain Mechanism Of Halogenation |
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61 | (7) |
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63 | (1) |
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63 | (1) |
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63 | (5) |
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68 | (8) |
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3.1 Definition And Classification |
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69 | (1) |
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70 | (3) |
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3.3 Some Facts About Double Bonds |
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73 | (1) |
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3.4 The Orbital Model Of A Double Bond; The Pi Bond |
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74 | (2) |
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A WORD ABOUT ...The Chemistry of Vision |
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76 | (22) |
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3.5 Cis-Trans Isomerism In Alkenes |
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76 | (2) |
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3.6 Addition And Substitution Reactions Compared |
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78 | (1) |
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3.7 Polar Addition Reactions |
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79 | (1) |
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3.7.a Addition of Halogens |
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79 | (1) |
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3.7.b Addition of Water (Hydration) |
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79 | (1) |
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80 | (1) |
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3.8 Addition Of Unsymmetric Reagents To Unsymmetric Alkenes; Markovnikovs Rule |
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80 | (2) |
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3.9 Mechanism Of Electrophilic Addition To Alkenes |
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82 | (2) |
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3.10 Markovnikov's Rule Explained |
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84 | (2) |
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3.11 Reaction Equilibrium: What Makes A Reaction Go? |
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86 | (1) |
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3.12 Reaction Rates: How Fast Does A Reaction Go? |
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87 | (3) |
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3.13 Hydroboration Of Alkenes |
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90 | (1) |
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3.14 Addition Of Hydrogen |
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91 | (1) |
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3.15 Additions To Conjugated Systems |
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92 | (3) |
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3.15.a Electrophilic Additions to Conjugated Dienes |
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92 | (2) |
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3.15.b Cycloacldition to Conjugated Dienes: The Diels-Alder Reaction |
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94 | (1) |
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3.16 Free-Radical Additions; Polyethylene |
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95 | (1) |
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96 | (2) |
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3.17.a Oxidation with Permanganate; a Chemical Test |
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97 | (1) |
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3.17.b Ozonolysis of Alkenes |
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97 | (1) |
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A WORD ABOUT ...Ethylene: Raw Material and Plant Hormone |
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98 | (4) |
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3.17.c Other Alkene Oxidations |
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99 | (1) |
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3.18 Some Facts About Triple Bonds |
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100 | (1) |
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3.19 The Orbital Model Of A Triple Bond |
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100 | (1) |
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3.20 Addition Reactions Of Alkynes |
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101 | (1) |
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A WORD ABOUT ...Petroleum, Gasoline, and Octane Number |
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102 | (3) |
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104 | (1) |
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A CLOSER LOOK AT ...Petroleum |
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105 | (23) |
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106 | (1) |
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107 | (1) |
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108 | (6) |
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114 | (14) |
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4.1 Some Facts About Benzene |
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115 | (1) |
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4.2 The Kekute Structure Of Benzene |
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116 | (1) |
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4.3 Resonance Model For Benzene |
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117 | (1) |
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4.4 Orbital Model For Benzene |
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117 | (1) |
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118 | (1) |
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4.6 Nomenclature Of Aromatic Compounds |
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118 | (3) |
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4.7 The Resonance Energy Of Benzene |
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121 | (1) |
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4.8 Electrophilic Aromatic Substitution |
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122 | (1) |
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4.9 The Mechanism Of Electrophilic Aromatic Substitution |
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123 | (5) |
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125 | (1) |
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126 | (1) |
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126 | (1) |
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4.9.d Alkylation and Acylation |
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127 | (1) |
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A WORD ABOUT ...Vitamin E: Tocopherols and Tocotrienols |
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128 | (8) |
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4.10 Ring-Activating And Ring-Deactivating Substituents |
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128 | (1) |
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4.11 Ortho, Para-Directing And Meta-Directing Groups |
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129 | (5) |
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4.11.a Ortho, Para-Directing Groups |
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130 | (2) |
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4.11.b Meta-Directing Groups |
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132 | (2) |
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4.11.c Substituent Effects on Reactivity |
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134 | (1) |
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4.12 The Importance Of Directing Effects In Synthesis |
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134 | (1) |
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4.13 Polycyclic Aromatic Hydrocarbons |
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135 | (1) |
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A WORD ABOUT ...Polycyclic Aromatic Hydrocarbons and Cancer |
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136 | (1) |
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A CLOSER LOOK AT ...Polycyclic Aromatic Hydrocarbons |
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137 | (1) |
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A WORD ABOUT ...C60, an Aromatic Sphere: The Fullerenes |
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138 | (22) |
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140 | (1) |
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141 | (1) |
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141 | (6) |
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147 | (13) |
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5.1 Chirality And Enantiomers |
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148 | (1) |
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5.2 Stereogenic Centers; The Stereogenic Carbon Atom |
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149 | (4) |
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5.3 Configuration And The R-S Convention |
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153 | (4) |
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5.4 The E-Z Convention For Cis-Trans Isomers |
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157 | (1) |
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5.5 Polarized Light And Optical Activity |
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158 | (2) |
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A WORD ABOUT ...Pasteur's Experiments and the van't Hoff-LeBel Explanation |
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160 | (12) |
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5.6 Properties Of Enantiomers |
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162 | (1) |
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5.7 Fischer Projection Formulas |
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163 | (2) |
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5.8 Compounds With More Than One Stereogenic Center; Diastereomers |
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165 | (2) |
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5.9 Meso Compounds; The Stereoisomers Of Tartaric Acid |
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167 | (2) |
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5.10 Stereochemistry: A Recap Of Definitions |
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169 | (1) |
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5.11 Stereochemistry And Chemical Reactions |
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170 | (2) |
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A WORD ABOUT ...Enantiomers and Biological Activity |
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172 | (2) |
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5.12 Resolution Of A Racemic Mixture |
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173 | (1) |
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A CLOSER LOOK AT ...Thalidomide |
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174 | (1) |
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A WORD ABOUT ...Green Chemistry: L-DOPA |
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175 | (18) |
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176 | (6) |
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6 Organic Halogen Compounds; Substitution and Elimination Reactions |
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182 | (11) |
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6.1 Nucleophilic Substitution |
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183 | (1) |
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6.2 Examples Of Nucleophilic Substitutions |
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183 | (4) |
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6.3 Nucleophilic Substitution Mechanisms |
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187 | (1) |
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187 | (3) |
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190 | (2) |
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6.6 The Sn1 And Sn2 Mechanisms Compared |
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192 | (1) |
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A WORD ABOUT ...SN2 Reactions in Nature: Biological Methylations |
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193 | (7) |
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6.7 Dehydrohalogenation, An Elimination Reaction; The E2 And E1 Mechanisms |
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195 | (1) |
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6.8 Substitution And Elimination In Competition |
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196 | (3) |
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196 | (1) |
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197 | (1) |
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197 | (2) |
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6.9 Polyhalogenated Aliphatic Compounds |
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199 | (1) |
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A WORD ABOUT ...CFCs, the Ozone Layer, and Trade-Offs |
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200 | (1) |
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A WORD ABOUT ...Halogenated Organic Compounds from the Sea |
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201 | (7) |
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202 | (1) |
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202 | (1) |
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203 | (3) |
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7 Alcohols, Phenols, and Thiols |
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206 | (2) |
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7.1 Nomenclature Of Alcohols |
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207 | (1) |
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A WORD ABOUT ...Industrial Alcohols |
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208 | (14) |
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7.2 Classification Of Alcohols |
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209 | (1) |
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7.3 Nomenclature Of Phenols |
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209 | (1) |
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7.4 Hydrogen Bonding In Alcohols And Phenols |
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210 | (1) |
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7.5 Acidity And Basicity Reviewed |
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211 | (2) |
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7.6 The Acidity Of Alcohols And Phenols |
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213 | (3) |
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7.7 The Basicity Of Alcohols And Phenols |
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216 | (1) |
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7.8 Dehydration Of Alcohols To Alkenes |
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216 | (2) |
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7.9 The Reaction Of Alcohols With Hydrogen Halides |
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218 | (1) |
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7.10 Other Ways To Prepare Alkyl Halides From Alcohols |
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219 | (1) |
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7.11 A Comparison Of Alcohols And Phenols |
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220 | (1) |
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7.12 Oxidation Of Alcohols To Aldehydes, Ketones, And Carboxylic Acids |
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220 | (2) |
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A WORD ABOUT ...Biologically Important Alcohols and Phenols |
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222 | (3) |
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7.13 Alcohols With More Than One Hydroxyl Group |
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223 | (1) |
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7.14 Aromatic Substitution In Phenols |
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224 | (1) |
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A WORD ABOUT ...Quinones and the Bombardier Beetle |
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225 | (3) |
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7.15 Oxidation Of Phenols |
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225 | (1) |
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7.16 Phenols As Antioxidants |
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226 | (1) |
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7.17 Thiols, The Sulfur Analogs Of Alcohols And Phenols |
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227 | (1) |
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A WORD ABOUT ...Hair---Curly or Straight |
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228 | (13) |
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229 | (1) |
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230 | (4) |
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234 | (7) |
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8.1 Nomenclature Of Ethers |
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235 | (1) |
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8.2 Physical Properties Of Ethers |
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236 | (1) |
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237 | (1) |
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8.4 The Grignard Reagent; An Organometallic Compound |
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237 | (3) |
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8.5 Preparation Of Ethers |
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240 | (1) |
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241 | (2) |
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242 | (1) |
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A WORD ABOUT ...Ether and Anesthesia |
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243 | (2) |
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244 | (1) |
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A WORD ABOUT ...The Gypsy Moth's Epoxide |
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245 | (29) |
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8.8 Reactions Of Epoxides |
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245 | (2) |
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247 | (6) |
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249 | (1) |
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250 | (3) |
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253 | (21) |
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9.1 Nomenclature Of Aldehydes And Ketones |
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254 | (1) |
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9.2 Some Common Aldehydes And Ketones |
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255 | (2) |
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9.3 Synthesis Of Aldehydes And Ketones |
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257 | (1) |
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9.4 Aldehydes And Ketones In Nature |
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258 | (1) |
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259 | (1) |
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9.6 Nucleophilic Addition To Carbonyl Groups: An Overview |
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260 | (1) |
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9.7 Addition Of Alcohols: Formation Of Hemiacetals And Acetals |
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261 | (3) |
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9.8 Addition Of Water; Hydration Of Aldehydes And Ketones |
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264 | (1) |
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9.9 Addition Of Grignard Reagents And Acetylides |
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265 | (3) |
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9.10 Addition Of Hydrogen Cyanide; Cyanohydrins |
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268 | (1) |
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9.11 Addition Of Nitrogen Nucleophiles |
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269 | (1) |
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9.12 Reduction Of Carbonyl Compounds |
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270 | (1) |
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9.13 Oxidation Of Carbonyl Compounds |
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271 | (1) |
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9.14 Keto-Enol Tautomerism |
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272 | (2) |
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A WORD ABOUT ...Tautomerism and Photochromism |
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274 | (5) |
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9.15 Acidity Of α-Hydrogens; The Enolate Anion |
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275 | (1) |
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9.16 Deuterium Exchange In Carbonyl Compounds |
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276 | (1) |
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9.17 The Aldol Condensation |
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277 | (1) |
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9.18 The Mixed Aldol Condensation |
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278 | (1) |
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A WORD ABOUT ...Water Treatment and the Chemistry of Enols/Enolates |
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279 | (20) |
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9.19 Commercial Syntheses Via The Aldol Condensation |
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280 | (7) |
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281 | (1) |
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282 | (1) |
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282 | (5) |
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10 Carboxylic Acids and Their Derivatives |
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287 | (12) |
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10.1 Nomenclature Of Acids |
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288 | (3) |
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10.2 Physical Properties Of Acids |
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291 | (1) |
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10.3 Acidity And Acidity Constants |
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292 | (1) |
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10.4 What Makes Carboxylic Acids Acidic? |
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293 | (2) |
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10.5 Effect Of Structure On Acidity; The Inductive Effect Revisited |
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295 | (1) |
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10.6 Conversion Of Acids To Salts |
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296 | (1) |
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10.7 Preparation Of Acids |
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296 | (3) |
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10.7.a Oxidation of Primary Alcohols and Aldehydes |
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296 | (1) |
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10.7.b Oxidation of Aromatic Side Chains |
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297 | (1) |
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10.7.c Reaction of Grignard Reagents with Carbon Dioxide |
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298 | (1) |
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10.7.d Hydrolysis of Cyanides (Nitriles) |
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298 | (1) |
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A WORD ABOUT ...Green Chemistry and Ibuprofen: A Case Study |
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299 | (13) |
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10.8 Carboxylic Acid Derivatives |
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300 | (1) |
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301 | (1) |
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10.10 Preparation Of Esters; Fischer Esterification |
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302 | (1) |
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10.11 The Mechanism Of Acid-Catalyzed Esterification; Nucleophilic Acyl Substitution |
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302 | (2) |
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304 | (1) |
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10.13 Saponification Of Esters |
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305 | (1) |
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10.14 Ammonolysis Of Esters |
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306 | (1) |
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10.15 Reaction Of Esters With Grignard Reagents |
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307 | (1) |
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10.16 Reduction Of Esters |
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307 | (1) |
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10.17 The Need For Activated Acyl Compounds |
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308 | (1) |
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309 | (1) |
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310 | (2) |
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A WORD ABOUT ...Thioesters, Nature's Acyl-Activating Groups |
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312 | (29) |
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313 | (2) |
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10.21 A Summary Of Carboxylic Acid Derivatives |
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315 | (2) |
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10.22 The α-Hydrogen Of Esters; The Claisen Condensation |
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317 | (10) |
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320 | (1) |
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321 | (1) |
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321 | (6) |
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11 Amines and Related Nitrogen Compounds |
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327 | (14) |
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11.1 Classification And Structure Of Amines |
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328 | (1) |
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11.2 Nomenclature Of Amines |
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329 | (1) |
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11.3 Physical Properties And Intermolecular Interactions Of Amines |
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330 | (1) |
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11.4 Preparation Of Amines; Alkylation Of Ammonia And Amines |
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331 | (2) |
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11.5 Preparation Of Amines; Reduction Of Nitrogen Compounds |
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333 | (2) |
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11.6 The Basicity Of Amines |
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335 | (3) |
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11.7 Comparison Of The Basicity And Acidity Of Amines And Amides |
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338 | (2) |
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11.8 Reaction Of Amines With Strong Acids; Amine Salts |
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340 | (1) |
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A WORD ABOUT ...Alkaloids and the Dart-Poison Frogs |
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341 | (27) |
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11.9 Chiral Amines As Resolving Agents |
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342 | (1) |
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11.10 Acylation Of Amines With Acid Derivatives |
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343 | (1) |
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11.11 Quaternary Ammonium Compounds |
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344 | (1) |
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11.12 Aromatic Diazonium Compounds |
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345 | (3) |
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11.13 Diazo Coupling; Azo Dyes |
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348 | (8) |
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350 | (1) |
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351 | (1) |
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351 | (5) |
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12 Spectroscopy and Structure Determination |
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356 | (12) |
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12.1 Principles Of Spectroscopy |
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357 | (2) |
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12.2 Nuclear Magnetic Resonance Spectroscopy |
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359 | (9) |
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12.2.a Measuring an NMR Spectrum |
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359 | (1) |
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12.2.b Chemical Shifts and Peak Areas |
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360 | (4) |
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12.2.c Spin-Spin Splitting |
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364 | (4) |
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A WORD ABOUT ...NMR in Biology and Medicine |
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368 | (13) |
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12.3 13C Nmr Spectroscopy |
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368 | (3) |
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12.4 Infrared Spectroscopy |
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371 | (4) |
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12.5 Visible And Ultraviolet Spectroscopy |
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375 | (2) |
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377 | (4) |
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A CLOSER LOOK AT ...Mass Spectrometry and Carbon Dating |
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381 | (21) |
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382 | (8) |
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13 Heterocyclic Compounds |
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390 | (12) |
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13.1 Pyridine: Bonding And Basicity |
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391 | (1) |
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13.2 Substitution In Pyridine |
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392 | (3) |
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13.3 Other Six-Membered Heterocycles |
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395 | (3) |
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13.4 Five-Membered Heterocycles: Furan, Pyrrole, And Thiophene |
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398 | (2) |
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13.5 Electrophilic Substitution In Furan, Pyrrole, And Thiophene |
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400 | (1) |
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13.6 Other Five-Membered Heterocycles: Azoles |
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401 | (1) |
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A WORD ABOUT ...Porphyrins: What Makes Blood Red and Grass Green? |
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402 | (3) |
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13.7 Fused-Ring Five-Membered Heterocycles: Indoles And Purines |
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403 | (2) |
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A WORD ABOUT ...Morphine and Other Nitrogen-Containing Drugs |
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405 | (16) |
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407 | (1) |
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408 | (1) |
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408 | (3) |
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411 | (10) |
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14.1 Classification Of Polymers |
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412 | (1) |
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14.2 Free-Radical Chain-Growth Polymerization |
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412 | (6) |
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14.3 Cationic Chain-Growth Polymerization |
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418 | (1) |
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14.4 Anionic Chain-Growth Polymerization |
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419 | (1) |
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14.5 Stereoregular Polymers; Ziegler-Natta Polymerization |
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420 | (1) |
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A WORD ABOUT ...Polyacetylene and Conducting Polymers |
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421 | (5) |
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14.6 Diene Polymers: Natural And Synthetic Rubber |
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422 | (2) |
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424 | (1) |
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14.8 Step-Growth Polymerization: Dacron And Nylon |
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425 | (1) |
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A WORD ABOUT ...Degradable Polymers |
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426 | (1) |
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A WORD ABOUT ...Aramids, the Latest in Polyamides |
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427 | (2) |
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A CLOSER LOOK AT ...Nylon |
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429 | (18) |
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14.9 Polyurethanes And Other Step-Growth Polymers |
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429 | (9) |
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433 | (1) |
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434 | (1) |
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435 | (3) |
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438 | (9) |
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15.1 Fats And Oils; Triesters Of Glycerol |
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439 | (3) |
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15.2 Hydrogenation Of Vegetable Oils |
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442 | (1) |
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15.3 Saponification Of Fats And Oils; Soap |
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443 | (1) |
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444 | (1) |
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15.5 Synthetic Detergents (Syndets) |
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445 | (2) |
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A WORD ABOUT ...Commercial Detergents |
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447 | (3) |
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449 | (1) |
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A WORD ABOUT ...Prostaglandins, Aspirin, and Pain |
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450 | (29) |
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15.7 Prostaglandins, Leukotrienes, And Lipoxins |
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451 | (1) |
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452 | (1) |
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15.9 Terpenes And Steroids |
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452 | (8) |
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457 | (1) |
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457 | (3) |
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460 | (19) |
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16.1 Definitions And Classification |
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461 | (1) |
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461 | (1) |
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16.3 Chirality In Monosaccharides; Fischer Projection Formulas And D,L-Sugars |
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462 | (4) |
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16.4 The Cyclic Hemiacetal Structures Of Monosaccharides |
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466 | (2) |
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16.5 Anomeric Carbons; Mutarotation |
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468 | (1) |
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16.6 Pyranose And Furanose Structures |
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469 | (1) |
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16.7 Conformations Of Pyranoses |
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470 | (1) |
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16.8 Esters And Ethers From Monosaccharides |
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471 | (1) |
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16.9 Reduction Of Monosaccharides |
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472 | (1) |
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16.10 Oxidation Of Monosaccharides |
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472 | (1) |
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16.11 Formation Of Glycosides From Monosaccharides |
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473 | (2) |
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475 | (4) |
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475 | (1) |
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476 | (1) |
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476 | (1) |
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|
477 | (2) |
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A WORD ABOUT ...Sweetness and Sweeteners |
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479 | (3) |
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480 | (2) |
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16.13.a Starch and Glycogen |
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480 | (1) |
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481 | (1) |
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A WORD ABOUT ...Fat Substitutes from Carbohydrates |
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|
482 | (2) |
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16.13.c Other Polysaccharides |
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|
483 | (1) |
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A WORD ABOUT ...Green Chemistry: Alternative Uses for Carbohydrates |
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|
484 | (19) |
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|
485 | (1) |
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485 | (1) |
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485 | (1) |
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16.17 Ascorbic Acid (Vitamin C) |
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486 | (6) |
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|
487 | (1) |
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|
488 | (4) |
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17 Amino Acids, Peptides, and Proteins |
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492 | (11) |
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17.1 Naturally Occurring Amino Acids |
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|
493 | (2) |
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17.2 The Acid--Base Properties Of Amino Acids |
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|
495 | (3) |
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17.3 The Acid--Base Properties Of Amino Acids With More Than One Acidic Or Basic Group |
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|
498 | (2) |
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|
500 | (1) |
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17.5 Reactions Of Amino Acids |
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|
500 | (1) |
|
17.6 The Ninhydrin Reaction |
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|
501 | (1) |
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|
502 | (1) |
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A WORD ABOUT ...Some Naturally Occurring Peptides |
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|
503 | (7) |
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504 | (1) |
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|
505 | (1) |
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17.10 The Primary Structure Of Proteins |
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|
505 | (4) |
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17.10.a Amino Acid Analysis |
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|
505 | (1) |
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17.10.b Sequence Determination |
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|
506 | (2) |
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17.10.c Cleavage of Selected Peptide Bonds |
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|
508 | (1) |
|
17.11 The Logic Of Sequence Determination |
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|
509 | (1) |
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A WORD ABOUT ...Protein Sequencing and Evolution |
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|
510 | (10) |
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|
511 | (4) |
|
17.13 Secondary Structure Of Proteins |
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|
515 | (2) |
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17.13.a Geometry of the Peptide Bond |
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|
515 | (1) |
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|
515 | (1) |
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17.13.c The a Helix and the Pleated Sheet |
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|
516 | (1) |
|
17.14 Tertiary Structure: Fibrous And Globular Proteins |
|
|
517 | (2) |
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17.15 Quaternary Protein Structure |
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|
519 | (1) |
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A CLOSER LOOK AT ...Nobel Laureates and Protein Chemistry |
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|
520 | (14) |
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|
521 | (1) |
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|
522 | (5) |
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18 Nucleotides and Nucleic Acids |
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|
527 | (7) |
|
18.1 The General Structure Of Nucleic Acids |
|
|
528 | (1) |
|
18.2 Components Of Deoxyribonucleic Acid (Dna) |
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528 | (1) |
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529 | (2) |
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|
531 | (1) |
|
18.5 The Primary Structure Of Dna |
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|
532 | (1) |
|
18.6 Sequencing Nucleic Acids |
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|
533 | (1) |
|
A WORD ABOUT ...DNA and Crime |
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|
534 | (5) |
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18.7 Laboratory Synthesis Of Nucleic Acids |
|
|
534 | (1) |
|
18.8 Secondary Dna Structure; The Double Helix |
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|
535 | (2) |
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|
537 | (2) |
|
A CLOSER LOOK AT ...The Polymerase Chain Reaction (PCR) |
|
|
539 | (3) |
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18.10 Ribonucleic Acids; Rna |
|
|
539 | (2) |
|
18.11 The Genetic Code And Protein Biosynthesis |
|
|
541 | (1) |
|
A WORD ABOUT ...The Human Genome |
|
|
542 | (2) |
|
A WORD ABOUT ...Nucleic Acids and Viruses |
|
|
544 | (9) |
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18.12 Other Biologically Important Nucleotides |
|
|
546 | (7) |
|
|
549 | (1) |
|
|
549 | (4) |
Appendix |
|
553 | (3) |
Index/Glossary |
|
556 | |